Water channel structure of bassanite at high air humidity: crystal structure of CaSO4·0.625H2O

Schmidt, H.; Paschke, I.; Freyer, D.; Voigt, W.

doi:10.1107/S0108768111041759

Water channel structure of bassanite at high air humidity: crystal structure of CaSO₄·0.625H₂O

H. Schmidt, I. Paschke, D. Freyer and W. Voigt

Structure analysis using single-crystal diffraction was carried out as a contribution to the dispute about the nature of the water channel structure of bassanite (CaSO₄·0.5H₂O). A recent result of Weiss & Bräu (2009) for the crystal structure of bassanite (monoclinic, space group C2) at ambient conditions of air humidity was confirmed. In the presence of high relative air humidity the crystal structure of bassanite transformed due to the incorporation of additional water of hydration. The crystal structure of CaSO₄·0.625H₂O was solved by single-crystal diffraction at 298 K and 75% relative air humidity. The experimental results provided an insight into both crystal structures. A model explaining the phase transition from CaSO₄·0.625H₂O to CaSO₄·0.5H₂O was derived. The monoclinic cell setting of CaSO₄·0.5H₂O and the trigonal cell setting of CaSO₄·0.625H₂O were confirmed by powder diffraction.

Keywords: bassanite; calcium sulfate subhydrate; single-crystal diffraction; powder diffraction; phase transition; high air humidity; gypsum.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768111041759/sn5106sup1.cif Contains datablocks caso40625, caso4_05, New_Global_Publ_Block
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768111041759/sn5106caso40625sup2.hkl Contains datablock hs_hh_nacl_301010_0m
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768111041759/sn5106caso4_05sup3.hkl Contains datablock tu_hklf5
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768111041759/sn5106Isup4.hkl Contains datablock I

Comment top

The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF.

For related literature, see [type here to add references to related literature].

Experimental top

(type here to add preparation details)

Computing details top

For both compounds, data collection: Apex2; cell refinement: Apex2; data reduction: Apex2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond 3.

Figures top

(caso40625) top

Crystal data top

CaH_1.25O_4.625S	D_x = 2.773 Mg m⁻³
M_r = 147.40	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₂21	Cell parameters from 943 reflections
Hall symbol: P 32 2"	θ = 1–27.5°
a = 13.8690 (4) Å	µ = 2.24 mm⁻¹
c = 12.7189 (1) Å	T = 296 K
V = 2118.70 (9) Å³	Needle, colourless
Z = 24	0.4 × 0.08 × 0.07 mm
F(000) = 1782

Data collection top

Bruker X8 Kappa. Apex2 diffractometer	3252 independent reflections
Radiation source: fine-focus sealed tube	2578 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω and phi scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: numerical ?	h = −17→17
T_min = 0.641, T_max = 0.896	k = −17→17
38925 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0478P)² + 2.072P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.027
3252 reflections	Δρ_max = 0.53 e Å⁻³
260 parameters	Δρ_min = −0.45 e Å⁻³
5 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
0 constraints	Absolute structure parameter: 0.00
Primary atom site location: structure-invariant direct methods

Crystal data top

CaH_1.25O_4.625S	Z = 24
M_r = 147.40	Mo Kα radiation
Trigonal, P3₂21	µ = 2.24 mm⁻¹
a = 13.8690 (4) Å	T = 296 K
c = 12.7189 (1) Å	0.4 × 0.08 × 0.07 mm
V = 2118.70 (9) Å³

Data collection top

Bruker X8 Kappa. Apex2 diffractometer	3252 independent reflections
Absorption correction: numerical ?	2578 reflections with I > 2σ(I)
T_min = 0.641, T_max = 0.896	R_int = 0.043
38925 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	Δρ_max = 0.53 e Å⁻³
S = 1.03	Δρ_min = −0.45 e Å⁻³
3252 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
260 parameters	Absolute structure parameter: 0.00
5 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.50186 (8)	0.77388 (9)	0.08244 (7)	0.0099 (3)
S2	0.77410 (9)	0.99600 (8)	0.41478 (8)	0.0103 (2)
S3	0.72701 (9)	0.72106 (9)	−0.24660 (7)	0.0096 (2)
S4	0.21741 (9)	0.72177 (9)	0.24212 (7)	0.0100 (2)
Ca1	0.76903 (10)	1.0000	0.1667	0.0126 (4)
Ca2	0.49029 (7)	0.77610 (8)	0.33088 (6)	0.0142 (2)
Ca3	0.74268 (9)	0.74268 (9)	0.0000	0.0122 (3)
Ca4	0.71424 (9)	0.71424 (9)	−0.5000	0.0148 (3)
Ca5	0.50256 (6)	0.77197 (8)	−0.16455 (6)	0.0135 (2)
Ca6	0.78358 (10)	1.0000	0.6667	0.0123 (3)
O1	0.6334 (2)	0.6938 (2)	−0.1736 (2)	0.0160 (6)
O2	0.1951 (2)	0.6233 (2)	0.1778 (2)	0.0166 (6)
O3	0.4352 (3)	0.7974 (2)	0.0072 (2)	0.0169 (6)
O4	0.7339 (3)	0.7999 (2)	−0.3272 (2)	0.0169 (7)
O5	0.5663 (2)	0.7355 (3)	0.0209 (2)	0.0206 (7)
O6	0.8680 (3)	1.0603 (2)	0.3412 (2)	0.0164 (6)
O7	0.8289 (2)	0.7705 (3)	−0.1815 (2)	0.0175 (7)
O8	0.7927 (2)	0.9169 (2)	0.4753 (2)	0.0180 (7)
O9	0.4298 (2)	0.6907 (2)	0.1594 (2)	0.0151 (7)
O10	0.2966 (2)	0.7407 (3)	0.3266 (2)	0.0167 (7)
O11	0.7664 (3)	1.0720 (2)	0.4902 (2)	0.0163 (7)
O12	0.6738 (2)	0.9397 (3)	0.3496 (2)	0.0178 (7)
O13	0.5778 (3)	0.8753 (2)	0.1423 (2)	0.0187 (7)
O14	0.1128 (3)	0.7027 (3)	0.2901 (2)	0.0200 (7)
O15	0.2623 (3)	0.8162 (2)	0.1692 (2)	0.0171 (7)
O16	0.5018 (3)	0.9431 (3)	−0.1888 (3)	0.0336 (9)
O17	0.9508 (4)	1.0000	0.6667	0.0560 (18)
O18	0.7094 (3)	0.6206 (2)	−0.3009 (2)	0.0199 (7)
O19	0.4803 (4)	0.9522 (4)	0.2989 (5)	0.0663 (15)
H1	0.453 (7)	0.985 (7)	0.258 (5)	0.099*
H2	0.545 (3)	0.982 (6)	0.277 (6)	0.099*
H3	0.564 (3)	0.993 (5)	−0.205 (6)	0.099*
H4	0.457 (6)	0.966 (7)	−0.181 (6)	0.099*
H5	1.005 (4)	1.060 (3)	0.678 (7)	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0110 (6)	0.0113 (5)	0.0065 (5)	0.0050 (4)	−0.0002 (4)	−0.0002 (4)
S2	0.0128 (5)	0.0122 (6)	0.0063 (5)	0.0066 (5)	0.0001 (4)	0.0002 (4)
S3	0.0118 (5)	0.0128 (5)	0.0061 (5)	0.0074 (5)	0.0005 (3)	−0.0007 (3)
S4	0.0119 (5)	0.0120 (5)	0.0067 (5)	0.0066 (4)	0.0004 (4)	−0.0006 (4)
Ca1	0.0162 (7)	0.0130 (7)	0.0076 (6)	0.0065 (4)	−0.0002 (2)	−0.0004 (5)
Ca2	0.0138 (5)	0.0189 (6)	0.0082 (4)	0.0071 (5)	−0.0005 (4)	−0.0012 (3)
Ca3	0.0154 (4)	0.0154 (4)	0.0074 (5)	0.0088 (5)	−0.0001 (2)	0.0001 (2)
Ca4	0.0187 (5)	0.0187 (5)	0.0115 (6)	0.0129 (6)	0.0008 (2)	−0.0008 (2)
Ca5	0.0134 (5)	0.0148 (7)	0.0102 (4)	0.0054 (5)	−0.0003 (3)	−0.0013 (3)
Ca6	0.0139 (5)	0.0130 (8)	0.0097 (6)	0.0065 (4)	0.0001 (2)	0.0003 (5)
O1	0.0150 (14)	0.0203 (16)	0.0126 (15)	0.0087 (13)	0.0053 (12)	0.0009 (13)
O2	0.0187 (16)	0.0169 (15)	0.0154 (14)	0.0097 (13)	0.0007 (13)	−0.0063 (13)
O3	0.0199 (17)	0.0231 (16)	0.0073 (13)	0.0104 (14)	−0.0038 (12)	−0.0006 (12)
O4	0.0250 (18)	0.0208 (17)	0.0063 (14)	0.0125 (15)	−0.0013 (12)	0.0032 (12)
O5	0.0184 (17)	0.035 (2)	0.0128 (15)	0.0163 (16)	0.0010 (13)	−0.0057 (13)
O6	0.0167 (16)	0.0199 (16)	0.0113 (14)	0.0083 (13)	0.0039 (12)	0.0015 (12)
O7	0.0160 (15)	0.0281 (18)	0.0111 (14)	0.0130 (14)	−0.0037 (11)	−0.0029 (13)
O8	0.0185 (16)	0.0187 (16)	0.0192 (15)	0.0112 (14)	0.0018 (13)	0.0058 (13)
O9	0.0158 (16)	0.0171 (16)	0.0052 (13)	0.0028 (13)	0.0040 (12)	0.0046 (11)
O10	0.0214 (16)	0.0265 (19)	0.0056 (14)	0.0145 (15)	−0.0035 (11)	−0.0002 (13)
O11	0.0229 (18)	0.0194 (17)	0.0103 (14)	0.0133 (15)	0.0005 (12)	−0.0021 (12)
O12	0.0155 (15)	0.0173 (17)	0.0165 (15)	0.0051 (14)	−0.0072 (12)	−0.0016 (13)
O13	0.0207 (17)	0.0133 (16)	0.0174 (16)	0.0050 (15)	−0.0063 (12)	−0.0069 (13)
O14	0.0131 (16)	0.0230 (18)	0.0239 (17)	0.0091 (14)	0.0101 (13)	0.0043 (14)
O15	0.0277 (18)	0.0183 (16)	0.0108 (15)	0.0156 (15)	0.0035 (12)	0.0054 (12)
O16	0.022 (2)	0.026 (2)	0.051 (2)	0.0103 (18)	0.0043 (18)	0.0107 (17)
O17	0.023 (2)	0.022 (3)	0.123 (6)	0.0108 (16)	−0.005 (2)	−0.011 (4)
O18	0.0257 (18)	0.0156 (16)	0.0200 (16)	0.0116 (14)	0.0021 (14)	−0.0047 (12)
O19	0.039 (3)	0.047 (3)	0.093 (4)	0.006 (2)	0.017 (3)	−0.015 (3)

Geometric parameters (Å, º) top

S1—O9	1.461 (3)	Ca3—O1	2.570 (3)
S1—O5	1.473 (3)	Ca3—O1^v	2.570 (3)
S1—O3	1.476 (3)	Ca3—S3^v	3.1479 (9)
S1—O13	1.478 (3)	Ca3—Ca1^vii	4.0074 (7)
S1—Ca5	3.1416 (11)	Ca4—O15^viii	2.403 (3)
S1—Ca2	3.1649 (12)	Ca4—O15^ix	2.403 (3)
S2—O8	1.465 (3)	Ca4—O4	2.448 (3)
S2—O12	1.465 (3)	Ca4—O4^x	2.448 (3)
S2—O11	1.467 (3)	Ca4—O8^xi	2.475 (3)
S2—O6	1.484 (3)	Ca4—O8^v	2.475 (3)
S2—Ca1	3.1576 (10)	Ca4—O18^x	2.831 (3)
S2—Ca6	3.2058 (10)	Ca4—O18	2.831 (3)
S3—O18	1.461 (3)	Ca4—S3^x	3.2267 (9)
S3—O4	1.467 (3)	Ca4—Ca6^xi	4.1610 (8)
S3—O7	1.478 (3)	Ca4—Ca6^xii	4.1611 (8)
S3—O1	1.483 (3)	Ca5—O16	2.398 (4)
S3—Ca3	3.1479 (9)	Ca5—O10^viii	2.403 (3)
S3—Ca4	3.2267 (9)	Ca5—O2ⁱ	2.433 (3)
S4—O10	1.463 (3)	Ca5—O11ⁱⁱⁱ	2.453 (3)
S4—O15	1.466 (3)	Ca5—O3	2.469 (3)
S4—O14	1.471 (3)	Ca5—O9ⁱ	2.486 (3)
S4—O2	1.487 (3)	Ca5—O1	2.539 (3)
S4—Ca2ⁱ	3.1154 (12)	Ca5—O5	2.654 (3)
S4—Ca5ⁱⁱ	3.3097 (12)	Ca5—O14^viii	3.059 (3)
Ca1—O13ⁱⁱⁱ	2.353 (3)	Ca5—S4^viii	3.3097 (12)
Ca1—O13	2.353 (3)	Ca5—Ca2^viii	4.0094 (12)
Ca1—O7^iv	2.390 (3)	Ca6—O17	2.319 (6)
Ca1—O7^v	2.390 (3)	Ca6—O14^vi	2.400 (3)
Ca1—O6	2.523 (3)	Ca6—O14^xiii	2.400 (3)
Ca1—O6ⁱⁱⁱ	2.523 (3)	Ca6—O4ⁱⁱⁱ	2.504 (3)
Ca1—O12	2.598 (3)	Ca6—O4^xiv	2.504 (3)
Ca1—O12ⁱⁱⁱ	2.598 (3)	Ca6—O11^xv	2.516 (3)
Ca1—S2ⁱⁱⁱ	3.1576 (10)	Ca6—O11	2.516 (3)
Ca1—Ca3^iv	4.0074 (7)	Ca6—O8^xv	2.723 (3)
Ca1—Ca3	4.0074 (7)	Ca6—O8	2.723 (3)
Ca2—O9	2.423 (3)	Ca6—S2^xv	3.2058 (10)
Ca2—O12	2.431 (3)	Ca6—Ca4^xvi	4.1611 (8)
Ca2—O18^v	2.438 (3)	O2—Ca5^vi	2.433 (3)
Ca2—O10	2.479 (3)	O2—Ca2ⁱ	2.549 (3)
Ca2—O15^vi	2.510 (3)	O3—Ca2ⁱ	2.560 (3)
Ca2—O19	2.548 (6)	O4—Ca6^xi	2.504 (3)
Ca2—O2^vi	2.549 (3)	O6—Ca3^iv	2.414 (3)
Ca2—O3^vi	2.560 (3)	O7—Ca1^vii	2.390 (3)
Ca2—O13	2.730 (3)	O8—Ca4^xiv	2.475 (3)
Ca2—S4^vi	3.1154 (12)	O9—Ca5^vi	2.486 (3)
Ca2—Ca5ⁱⁱ	4.0094 (12)	O10—Ca5ⁱⁱ	2.403 (3)
Ca3—O5	2.413 (3)	O11—Ca5ⁱⁱⁱ	2.453 (3)
Ca3—O5^v	2.413 (3)	O14—Ca6ⁱ	2.400 (3)
Ca3—O6ⁱⁱⁱ	2.414 (3)	O14—Ca5ⁱⁱ	3.059 (3)
Ca3—O6^vii	2.414 (3)	O15—Ca4ⁱⁱ	2.403 (3)
Ca3—O7^v	2.539 (3)	O15—Ca2ⁱ	2.510 (3)
Ca3—O7	2.539 (3)	O18—Ca2^v	2.438 (3)

O9—S1—O5	111.69 (19)	O7—Ca3—Ca1	121.30 (7)
O9—S1—O3	110.64 (18)	O1—Ca3—Ca1	117.93 (7)
O5—S1—O3	107.13 (17)	O1^v—Ca3—Ca1	87.16 (6)
O9—S1—O13	106.69 (18)	S3—Ca3—Ca1	125.67 (3)
O5—S1—O13	110.20 (18)	S3^v—Ca3—Ca1	59.839 (19)
O3—S1—O13	110.53 (19)	Ca1^vii—Ca3—Ca1	121.20 (5)
O9—S1—Ca5	131.83 (12)	O15^viii—Ca4—O15^ix	133.50 (16)
O5—S1—Ca5	57.34 (12)	O15^viii—Ca4—O4	78.96 (10)
O3—S1—Ca5	50.06 (12)	O15^ix—Ca4—O4	115.28 (9)
O13—S1—Ca5	121.27 (13)	O15^viii—Ca4—O4^x	115.28 (9)
O9—S1—Ca2	47.23 (11)	O15^ix—Ca4—O4^x	78.96 (10)
O5—S1—Ca2	125.26 (13)	O4—Ca4—O4^x	145.27 (15)
O3—S1—Ca2	127.24 (13)	O15^viii—Ca4—O8^xi	76.05 (10)
O13—S1—Ca2	59.48 (13)	O15^ix—Ca4—O8^xi	149.65 (11)
Ca5—S1—Ca2	177.23 (4)	O4—Ca4—O8^xi	71.57 (10)
O8—S2—O12	111.95 (18)	O4^x—Ca4—O8^xi	81.13 (10)
O8—S2—O11	107.33 (17)	O15^viii—Ca4—O8^v	149.65 (11)
O12—S2—O11	111.24 (19)	O15^ix—Ca4—O8^v	76.05 (10)
O8—S2—O6	110.52 (18)	O4—Ca4—O8^v	81.13 (10)
O12—S2—O6	106.10 (17)	O4^x—Ca4—O8^v	71.57 (10)
O11—S2—O6	109.72 (17)	O8^xi—Ca4—O8^v	76.04 (14)
O8—S2—Ca1	123.50 (13)	O15^viii—Ca4—O18^x	64.58 (9)
O12—S2—Ca1	54.55 (12)	O15^ix—Ca4—O18^x	103.82 (9)
O11—S2—Ca1	129.07 (12)	O4—Ca4—O18^x	138.87 (9)
O6—S2—Ca1	51.71 (12)	O4^x—Ca4—O18^x	52.46 (9)
O8—S2—Ca6	57.79 (12)	O8^xi—Ca4—O18^x	81.33 (9)
O12—S2—Ca6	126.50 (13)	O8^v—Ca4—O18^x	122.04 (9)
O11—S2—Ca6	49.58 (12)	O15^viii—Ca4—O18	103.82 (9)
O6—S2—Ca6	127.10 (13)	O15^ix—Ca4—O18	64.58 (9)
Ca1—S2—Ca6	178.27 (3)	O4—Ca4—O18	52.46 (9)
O18—S3—O4	107.32 (18)	O4^x—Ca4—O18	138.87 (9)
O18—S3—O7	111.83 (18)	O8^xi—Ca4—O18	122.04 (9)
O4—S3—O7	110.80 (19)	O8^v—Ca4—O18	81.33 (9)
O18—S3—O1	110.19 (19)	O18^x—Ca4—O18	152.10 (13)
O4—S3—O1	110.49 (18)	O15^viii—Ca4—S3	91.36 (7)
O7—S3—O1	106.25 (16)	O15^ix—Ca4—S3	90.54 (7)
O18—S3—Ca3	122.15 (13)	O4—Ca4—S3	25.55 (7)
O4—S3—Ca3	130.52 (12)	O4^x—Ca4—S3	151.30 (7)
O7—S3—Ca3	52.62 (11)	O8^xi—Ca4—S3	96.15 (7)
O1—S3—Ca3	53.89 (12)	O8^v—Ca4—S3	80.01 (7)
O18—S3—Ca4	61.29 (13)	O18^x—Ca4—S3	155.78 (6)
O4—S3—Ca4	46.04 (12)	O18—Ca4—S3	26.92 (6)
O7—S3—Ca4	126.81 (12)	O15^viii—Ca4—S3^x	90.54 (7)
O1—S3—Ca4	126.11 (12)	O15^ix—Ca4—S3^x	91.36 (7)
Ca3—S3—Ca4	176.55 (4)	O4—Ca4—S3^x	151.30 (7)
O10—S4—O15	111.06 (19)	O4^x—Ca4—S3^x	25.55 (7)
O10—S4—O14	108.16 (18)	O8^xi—Ca4—S3^x	80.01 (7)
O15—S4—O14	111.27 (18)	O8^v—Ca4—S3^x	96.15 (7)
O10—S4—O2	111.22 (18)	O18^x—Ca4—S3^x	26.92 (6)
O15—S4—O2	105.85 (17)	O18—Ca4—S3^x	155.78 (6)
O14—S4—O2	109.29 (19)	S3—Ca4—S3^x	175.18 (6)
O10—S4—Ca2ⁱ	135.05 (13)	O15^viii—Ca4—Ca6^xi	69.69 (7)
O15—S4—Ca2ⁱ	52.53 (12)	O15^ix—Ca4—Ca6^xi	144.51 (7)
O14—S4—Ca2ⁱ	116.80 (14)	O4—Ca4—Ca6^xi	33.26 (7)
O2—S4—Ca2ⁱ	54.22 (12)	O4^x—Ca4—Ca6^xi	118.88 (8)
O10—S4—Ca5ⁱⁱ	40.89 (12)	O8^xi—Ca4—Ca6^xi	38.93 (7)
O15—S4—Ca5ⁱⁱ	127.46 (12)	O8^v—Ca4—Ca6^xi	81.12 (8)
O14—S4—Ca5ⁱⁱ	67.28 (13)	O18^x—Ca4—Ca6^xi	111.29 (6)
O2—S4—Ca5ⁱⁱ	124.69 (12)	O18—Ca4—Ca6^xi	85.54 (6)
Ca2ⁱ—S4—Ca5ⁱⁱ	175.88 (4)	S3—Ca4—Ca6^xi	58.67 (2)
O13ⁱⁱⁱ—Ca1—O13	81.10 (16)	S3^x—Ca4—Ca6^xi	118.04 (3)
O13ⁱⁱⁱ—Ca1—O7^iv	81.17 (11)	O15^viii—Ca4—Ca6^xii	144.52 (7)
O13—Ca1—O7^iv	156.98 (11)	O15^ix—Ca4—Ca6^xii	69.69 (7)
O13ⁱⁱⁱ—Ca1—O7^v	156.98 (12)	O4—Ca4—Ca6^xii	118.88 (8)
O13—Ca1—O7^v	81.17 (11)	O4^x—Ca4—Ca6^xii	33.26 (7)
O7^iv—Ca1—O7^v	119.39 (17)	O8^xi—Ca4—Ca6^xii	81.12 (8)
O13ⁱⁱⁱ—Ca1—O6	89.35 (10)	O8^v—Ca4—Ca6^xii	38.93 (7)
O13—Ca1—O6	125.89 (10)	O18^x—Ca4—Ca6^xii	85.54 (6)
O7^iv—Ca1—O6	68.39 (9)	O18—Ca4—Ca6^xii	111.29 (6)
O7^v—Ca1—O6	89.23 (10)	S3—Ca4—Ca6^xii	118.04 (3)
O13ⁱⁱⁱ—Ca1—O6ⁱⁱⁱ	125.89 (10)	S3^x—Ca4—Ca6^xii	58.67 (2)
O13—Ca1—O6ⁱⁱⁱ	89.35 (10)	Ca6^xi—Ca4—Ca6^xii	107.43 (5)
O7^iv—Ca1—O6ⁱⁱⁱ	89.23 (10)	O16—Ca5—O10^viii	96.00 (13)
O7^v—Ca1—O6ⁱⁱⁱ	68.39 (9)	O16—Ca5—O2ⁱ	141.21 (11)
O6—Ca1—O6ⁱⁱⁱ	135.55 (14)	O10^viii—Ca5—O2ⁱ	71.62 (10)
O13ⁱⁱⁱ—Ca1—O12	78.20 (10)	O16—Ca5—O11ⁱⁱⁱ	70.83 (11)
O13—Ca1—O12	71.14 (10)	O10^viii—Ca5—O11ⁱⁱⁱ	112.87 (10)
O7^iv—Ca1—O12	119.04 (9)	O2ⁱ—Ca5—O11ⁱⁱⁱ	147.97 (11)
O7^v—Ca1—O12	82.24 (10)	O16—Ca5—O3	77.50 (12)
O6—Ca1—O12	54.78 (9)	O10^viii—Ca5—O3	143.29 (10)
O6ⁱⁱⁱ—Ca1—O12	147.07 (9)	O2ⁱ—Ca5—O3	90.83 (10)
O13ⁱⁱⁱ—Ca1—O12ⁱⁱⁱ	71.14 (10)	O11ⁱⁱⁱ—Ca5—O3	99.18 (10)
O13—Ca1—O12ⁱⁱⁱ	78.20 (10)	O16—Ca5—O9ⁱ	68.74 (11)
O7^iv—Ca1—O12ⁱⁱⁱ	82.24 (10)	O10^viii—Ca5—O9ⁱ	76.34 (10)
O7^v—Ca1—O12ⁱⁱⁱ	119.04 (9)	O2ⁱ—Ca5—O9ⁱ	72.59 (11)
O6—Ca1—O12ⁱⁱⁱ	147.07 (9)	O11ⁱⁱⁱ—Ca5—O9ⁱ	139.28 (12)
O6ⁱⁱⁱ—Ca1—O12ⁱⁱⁱ	54.78 (9)	O3—Ca5—O9ⁱ	67.58 (9)
O12—Ca1—O12ⁱⁱⁱ	139.36 (14)	O16—Ca5—O1	140.73 (11)
O13ⁱⁱⁱ—Ca1—S2	84.34 (8)	O10^viii—Ca5—O1	87.73 (11)
O13—Ca1—S2	98.38 (8)	O2ⁱ—Ca5—O1	76.89 (10)
O7^iv—Ca1—S2	94.36 (7)	O11ⁱⁱⁱ—Ca5—O1	71.76 (10)
O7^v—Ca1—S2	83.83 (7)	O3—Ca5—O1	120.20 (9)
O6—Ca1—S2	27.50 (7)	O9ⁱ—Ca5—O1	148.70 (11)
O6ⁱⁱⁱ—Ca1—S2	149.71 (8)	O16—Ca5—O5	117.98 (13)
O12—Ca1—S2	27.34 (6)	O10^viii—Ca5—O5	145.97 (12)
O12ⁱⁱⁱ—Ca1—S2	155.48 (7)	O2ⁱ—Ca5—O5	81.86 (10)
O13ⁱⁱⁱ—Ca1—S2ⁱⁱⁱ	98.38 (8)	O11ⁱⁱⁱ—Ca5—O5	79.32 (10)
O13—Ca1—S2ⁱⁱⁱ	84.34 (8)	O3—Ca5—O5	55.02 (9)
O7^iv—Ca1—S2ⁱⁱⁱ	83.83 (7)	O9ⁱ—Ca5—O5	116.02 (9)
O7^v—Ca1—S2ⁱⁱⁱ	94.36 (7)	O1—Ca5—O5	65.30 (9)
O6—Ca1—S2ⁱⁱⁱ	149.71 (8)	O16—Ca5—O14^viii	64.30 (12)
O6ⁱⁱⁱ—Ca1—S2ⁱⁱⁱ	27.50 (7)	O10^viii—Ca5—O14^viii	49.82 (9)
O12—Ca1—S2ⁱⁱⁱ	155.48 (7)	O2ⁱ—Ca5—O14^viii	120.55 (9)
O12ⁱⁱⁱ—Ca1—S2ⁱⁱⁱ	27.34 (6)	O11ⁱⁱⁱ—Ca5—O14^viii	66.59 (9)
S2—Ca1—S2ⁱⁱⁱ	176.44 (6)	O3—Ca5—O14^viii	141.69 (10)
O13ⁱⁱⁱ—Ca1—Ca3^iv	73.04 (8)	O9ⁱ—Ca5—O14^viii	99.36 (9)
O13—Ca1—Ca3^iv	146.08 (8)	O1—Ca5—O14^viii	90.11 (9)
O7^iv—Ca1—Ca3^iv	36.86 (6)	O5—Ca5—O14^viii	143.14 (9)
O7^v—Ca1—Ca3^iv	116.28 (9)	O16—Ca5—S1	96.82 (11)
O6—Ca1—Ca3^iv	34.84 (7)	O10^viii—Ca5—S1	158.52 (8)
O6ⁱⁱⁱ—Ca1—Ca3^iv	123.57 (7)	O2ⁱ—Ca5—S1	87.66 (7)
O12—Ca1—Ca3^iv	82.21 (6)	O11ⁱⁱⁱ—Ca5—S1	87.65 (7)
O12ⁱⁱⁱ—Ca1—Ca3^iv	112.43 (7)	O3—Ca5—S1	27.28 (7)
S2—Ca1—Ca3^iv	58.134 (19)	O9ⁱ—Ca5—S1	92.40 (7)
S2ⁱⁱⁱ—Ca1—Ca3^iv	120.39 (2)	O1—Ca5—S1	93.15 (7)
O13ⁱⁱⁱ—Ca1—Ca3	146.08 (8)	O5—Ca5—S1	27.84 (6)
O13—Ca1—Ca3	73.04 (8)	O14^viii—Ca5—S1	151.54 (7)
O7^iv—Ca1—Ca3	116.28 (9)	O16—Ca5—S4^viii	80.28 (11)
O7^v—Ca1—Ca3	36.86 (6)	O10^viii—Ca5—S4^viii	23.48 (7)
O6—Ca1—Ca3	123.57 (7)	O2ⁱ—Ca5—S4^viii	94.75 (7)
O6ⁱⁱⁱ—Ca1—Ca3	34.84 (7)	O11ⁱⁱⁱ—Ca5—S4^viii	91.15 (7)
O12—Ca1—Ca3	112.43 (7)	O3—Ca5—S4^viii	150.76 (8)
O12ⁱⁱⁱ—Ca1—Ca3	82.21 (6)	O9ⁱ—Ca5—S4^viii	86.77 (7)
S2—Ca1—Ca3	120.39 (2)	O1—Ca5—S4^viii	88.99 (7)
S2ⁱⁱⁱ—Ca1—Ca3	58.134 (19)	O5—Ca5—S4^viii	154.22 (7)
Ca3^iv—Ca1—Ca3	138.53 (5)	O14^viii—Ca5—S4^viii	26.34 (5)
O9—Ca2—O12	119.30 (10)	S1—Ca5—S4^viii	177.09 (4)
O9—Ca2—O18^v	79.31 (11)	O16—Ca5—Ca2^viii	117.10 (10)
O12—Ca2—O18^v	74.95 (11)	O10^viii—Ca5—Ca2^viii	35.41 (7)
O9—Ca2—O10	78.91 (11)	O2ⁱ—Ca5—Ca2^viii	37.42 (7)
O12—Ca2—O10	135.44 (12)	O11ⁱⁱⁱ—Ca5—Ca2^viii	144.37 (7)
O18^v—Ca2—O10	149.05 (11)	O3—Ca5—Ca2^viii	116.39 (7)
O9—Ca2—O15^vi	138.73 (12)	O9ⁱ—Ca5—Ca2^viii	63.73 (8)
O12—Ca2—O15^vi	78.32 (10)	O1—Ca5—Ca2^viii	87.69 (7)
O18^v—Ca2—O15^vi	69.47 (10)	O5—Ca5—Ca2^viii	118.68 (7)
O10—Ca2—O15^vi	116.02 (9)	O14^viii—Ca5—Ca2^viii	85.22 (6)
O9—Ca2—O19	98.84 (16)	S1—Ca5—Ca2^viii	123.14 (3)
O12—Ca2—O19	69.78 (14)	S4^viii—Ca5—Ca2^viii	58.88 (2)
O18^v—Ca2—O19	138.16 (13)	O17—Ca6—O14^vi	142.47 (8)
O10—Ca2—O19	67.24 (13)	O17—Ca6—O14^xiii	142.47 (8)
O15^vi—Ca2—O19	122.41 (15)	O14^vi—Ca6—O14^xiii	75.06 (15)
O9—Ca2—O2^vi	145.53 (10)	O17—Ca6—O4ⁱⁱⁱ	73.79 (8)
O12—Ca2—O2^vi	92.53 (10)	O14^vi—Ca6—O4ⁱⁱⁱ	139.11 (11)
O18^v—Ca2—O2^vi	124.96 (10)	O14^xiii—Ca6—O4ⁱⁱⁱ	71.75 (11)
O10—Ca2—O2^vi	68.46 (9)	O17—Ca6—O4^xiv	73.79 (8)
O15^vi—Ca2—O2^vi	55.50 (9)	O14^vi—Ca6—O4^xiv	71.75 (11)
O19—Ca2—O2^vi	78.99 (14)	O14^xiii—Ca6—O4^xiv	139.11 (12)
O9—Ca2—O3^vi	67.08 (9)	O4ⁱⁱⁱ—Ca6—O4^xiv	147.58 (16)
O12—Ca2—O3^vi	150.16 (11)	O17—Ca6—O11^xv	107.03 (7)
O18^v—Ca2—O3^vi	78.18 (10)	O14^vi—Ca6—O11^xv	77.19 (10)
O10—Ca2—O3^vi	73.21 (11)	O14^xiii—Ca6—O11^xv	75.95 (11)
O15^vi—Ca2—O3^vi	80.34 (10)	O4ⁱⁱⁱ—Ca6—O11^xv	116.05 (9)
O19—Ca2—O3^vi	139.98 (13)	O4^xiv—Ca6—O11^xv	74.00 (10)
O2^vi—Ca2—O3^vi	92.33 (10)	O17—Ca6—O11	107.03 (7)
O9—Ca2—O13	54.08 (9)	O14^vi—Ca6—O11	75.95 (11)
O12—Ca2—O13	67.76 (9)	O14^xiii—Ca6—O11	77.19 (10)
O18^v—Ca2—O13	80.02 (11)	O4ⁱⁱⁱ—Ca6—O11	74.00 (10)
O10—Ca2—O13	104.18 (10)	O4^xiv—Ca6—O11	116.05 (9)
O15^vi—Ca2—O13	139.16 (9)	O11^xv—Ca6—O11	145.94 (15)
O19—Ca2—O13	66.41 (14)	O17—Ca6—O8^xv	75.04 (7)
O2^vi—Ca2—O13	144.21 (11)	O14^vi—Ca6—O8^xv	128.05 (10)
O3^vi—Ca2—O13	119.88 (9)	O14^xiii—Ca6—O8^xv	78.06 (10)
O9—Ca2—S4^vi	156.10 (8)	O4ⁱⁱⁱ—Ca6—O8^xv	66.67 (9)
O12—Ca2—S4^vi	81.61 (8)	O4^xiv—Ca6—O8^xv	104.59 (9)
O18^v—Ca2—S4^vi	96.87 (8)	O11^xv—Ca6—O8^xv	53.41 (9)
O10—Ca2—S4^vi	94.23 (7)	O11—Ca6—O8^xv	138.36 (9)
O15^vi—Ca2—S4^vi	27.62 (7)	O17—Ca6—O8	75.04 (7)
O19—Ca2—S4^vi	99.48 (13)	O14^vi—Ca6—O8	78.06 (10)
O2^vi—Ca2—S4^vi	28.24 (7)	O14^xiii—Ca6—O8	128.05 (10)
O3^vi—Ca2—S4^vi	89.02 (7)	O4ⁱⁱⁱ—Ca6—O8	104.59 (9)
O13—Ca2—S4^vi	149.03 (7)	O4^xiv—Ca6—O8	66.67 (9)
O9—Ca2—S1	26.28 (7)	O11^xv—Ca6—O8	138.36 (9)
O12—Ca2—S1	94.14 (7)	O11—Ca6—O8	53.41 (9)
O18^v—Ca2—S1	77.83 (8)	O8^xv—Ca6—O8	150.08 (13)
O10—Ca2—S1	91.80 (7)	O17—Ca6—S2^xv	91.85 (3)
O15^vi—Ca2—S1	147.29 (7)	O14^vi—Ca6—S2^xv	102.22 (8)
O19—Ca2—S1	82.94 (13)	O14^xiii—Ca6—S2^xv	74.75 (8)
O2^vi—Ca2—S1	157.21 (7)	O4ⁱⁱⁱ—Ca6—S2^xv	91.48 (7)
O3^vi—Ca2—S1	92.64 (7)	O4^xiv—Ca6—S2^xv	89.56 (7)
O13—Ca2—S1	27.80 (6)	O11^xv—Ca6—S2^xv	26.35 (7)
S4^vi—Ca2—S1	173.97 (4)	O11—Ca6—S2^xv	151.30 (7)
O9—Ca2—Ca5ⁱⁱ	110.31 (8)	O8^xv—Ca6—S2^xv	27.07 (6)
O12—Ca2—Ca5ⁱⁱ	122.55 (8)	O8—Ca6—S2^xv	155.11 (7)
O18^v—Ca2—Ca5ⁱⁱ	144.27 (8)	O17—Ca6—S2	91.85 (3)
O10—Ca2—Ca5ⁱⁱ	34.17 (6)	O14^vi—Ca6—S2	74.75 (8)
O15^vi—Ca2—Ca5ⁱⁱ	83.22 (6)	O14^xiii—Ca6—S2	102.22 (8)
O19—Ca2—Ca5ⁱⁱ	75.99 (11)	O4ⁱⁱⁱ—Ca6—S2	89.56 (7)
O2^vi—Ca2—Ca5ⁱⁱ	35.43 (7)	O4^xiv—Ca6—S2	91.48 (7)
O3^vi—Ca2—Ca5ⁱⁱ	74.81 (7)	O11^xv—Ca6—S2	151.30 (7)
O13—Ca2—Ca5ⁱⁱ	134.14 (8)	O11—Ca6—S2	26.35 (7)
S4^vi—Ca2—Ca5ⁱⁱ	60.06 (2)	O8^xv—Ca6—S2	155.11 (7)
S1—Ca2—Ca5ⁱⁱ	125.96 (3)	O8—Ca6—S2	27.07 (6)
O5—Ca3—O5^v	116.35 (16)	S2^xv—Ca6—S2	176.29 (6)
O5—Ca3—O6ⁱⁱⁱ	81.27 (10)	O17—Ca6—Ca4^xvi	75.81 (2)
O5^v—Ca3—O6ⁱⁱⁱ	161.06 (11)	O14^vi—Ca6—Ca4^xvi	140.96 (8)
O5—Ca3—O6^vii	161.06 (11)	O14^xiii—Ca6—Ca4^xvi	67.18 (8)
O5^v—Ca3—O6^vii	81.27 (10)	O4ⁱⁱⁱ—Ca6—Ca4^xvi	32.41 (6)
O6ⁱⁱⁱ—Ca3—O6^vii	82.33 (14)	O4^xiv—Ca6—Ca4^xvi	135.02 (8)
O5—Ca3—O7^v	80.28 (10)	O11^xv—Ca6—Ca4^xvi	84.29 (7)
O5^v—Ca3—O7^v	119.82 (9)	O11—Ca6—Ca4^xvi	104.07 (7)
O6ⁱⁱⁱ—Ca3—O7^v	67.78 (9)	O8^xv—Ca6—Ca4^xvi	34.81 (6)
O6^vii—Ca3—O7^v	84.80 (10)	O8—Ca6—Ca4^xvi	133.98 (7)
O5—Ca3—O7	119.82 (9)	S2^xv—Ca6—Ca4^xvi	59.099 (19)
O5^v—Ca3—O7	80.28 (10)	S2—Ca6—Ca4^xvi	121.97 (2)
O6ⁱⁱⁱ—Ca3—O7	84.80 (10)	S3—O1—Ca5	129.88 (17)
O6^vii—Ca3—O7	67.78 (9)	S3—O1—Ca3	98.32 (14)
O7^v—Ca3—O7	143.71 (14)	Ca5—O1—Ca3	107.55 (10)
O5—Ca3—O1	68.38 (9)	S4—O2—Ca5^vi	135.82 (18)
O5^v—Ca3—O1	85.32 (10)	S4—O2—Ca2ⁱ	97.54 (15)
O6ⁱⁱⁱ—Ca3—O1	95.73 (9)	Ca5^vi—O2—Ca2ⁱ	107.15 (10)
O6^vii—Ca3—O1	122.86 (9)	S1—O3—Ca5	102.66 (15)
O7^v—Ca3—O1	146.71 (9)	S1—O3—Ca2ⁱ	129.33 (17)
O7—Ca3—O1	55.24 (9)	Ca5—O3—Ca2ⁱ	108.84 (11)
O5—Ca3—O1^v	85.32 (10)	S3—O4—Ca4	108.42 (16)
O5^v—Ca3—O1^v	68.38 (9)	S3—O4—Ca6^xi	136.66 (17)
O6ⁱⁱⁱ—Ca3—O1^v	122.86 (9)	Ca4—O4—Ca6^xi	114.33 (11)
O6^vii—Ca3—O1^v	95.73 (9)	S1—O5—Ca3	146.02 (19)
O7^v—Ca3—O1^v	55.24 (9)	S1—O5—Ca5	94.82 (14)
O7—Ca3—O1^v	146.71 (9)	Ca3—O5—Ca5	108.76 (11)
O1—Ca3—O1^v	129.48 (13)	S2—O6—Ca3^iv	130.32 (16)
O5—Ca3—S3	94.90 (7)	S2—O6—Ca1	100.79 (15)
O5^v—Ca3—S3	80.09 (7)	Ca3^iv—O6—Ca1	108.51 (10)
O6ⁱⁱⁱ—Ca3—S3	92.02 (7)	S3—O7—Ca1^vii	139.76 (18)
O6^vii—Ca3—S3	95.08 (7)	S3—O7—Ca3	99.82 (14)
O7^v—Ca3—S3	159.67 (7)	Ca1^vii—O7—Ca3	108.75 (10)
O7—Ca3—S3	27.56 (6)	S2—O8—Ca4^xiv	140.84 (18)
O1—Ca3—S3	27.79 (6)	S2—O8—Ca6	95.14 (15)
O1^v—Ca3—S3	144.55 (7)	Ca4^xiv—O8—Ca6	106.26 (10)
O5—Ca3—S3^v	80.09 (7)	S1—O9—Ca2	106.49 (15)
O5^v—Ca3—S3^v	94.90 (7)	S1—O9—Ca5^vi	140.65 (17)
O6ⁱⁱⁱ—Ca3—S3^v	95.08 (7)	Ca2—O9—Ca5^vi	112.85 (11)
O6^vii—Ca3—S3^v	92.02 (7)	S4—O10—Ca5ⁱⁱ	115.63 (17)
O7^v—Ca3—S3^v	27.56 (6)	S4—O10—Ca2	133.90 (17)
O7—Ca3—S3^v	159.67 (7)	Ca5ⁱⁱ—O10—Ca2	110.43 (11)
O1—Ca3—S3^v	144.54 (7)	S2—O11—Ca5ⁱⁱⁱ	141.19 (17)
O1^v—Ca3—S3^v	27.79 (6)	S2—O11—Ca6	104.07 (15)
S3—Ca3—S3^v	170.57 (6)	Ca5ⁱⁱⁱ—O11—Ca6	114.53 (11)
O5—Ca3—Ca1^vii	154.20 (7)	S2—O12—Ca2	145.59 (19)
O5^v—Ca3—Ca1^vii	67.51 (7)	S2—O12—Ca1	98.11 (15)
O6ⁱⁱⁱ—Ca3—Ca1^vii	93.62 (8)	Ca2—O12—Ca1	109.84 (11)
O6^vii—Ca3—Ca1^vii	36.66 (7)	S1—O13—Ca1	140.5 (2)
O7^v—Ca3—Ca1^vii	121.30 (8)	S1—O13—Ca2	92.71 (15)
O7—Ca3—Ca1^vii	34.39 (6)	Ca1—O13—Ca2	107.94 (11)
O1—Ca3—Ca1^vii	87.16 (6)	S4—O14—Ca6ⁱ	145.68 (19)
O1^v—Ca3—Ca1^vii	117.93 (7)	S4—O14—Ca5ⁱⁱ	86.38 (14)
S3—Ca3—Ca1^vii	59.84 (2)	Ca6ⁱ—O14—Ca5ⁱⁱ	99.24 (10)
S3^v—Ca3—Ca1^vii	125.67 (3)	S4—O15—Ca4ⁱⁱ	136.74 (17)
O5—Ca3—Ca1	67.51 (7)	S4—O15—Ca2ⁱ	99.85 (14)
O5^v—Ca3—Ca1	154.20 (7)	Ca4ⁱⁱ—O15—Ca2ⁱ	117.70 (11)
O6ⁱⁱⁱ—Ca3—Ca1	36.66 (7)	S3—O18—Ca2^v	146.74 (19)
O6^vii—Ca3—Ca1	93.62 (8)	S3—O18—Ca4	91.80 (14)
O7^v—Ca3—Ca1	34.39 (6)	Ca2^v—O18—Ca4	105.62 (11)

Symmetry codes: (i) −y+1, x−y+1, z−1/3; (ii) −y+1, x−y+1, z+2/3; (iii) x−y+1, −y+2, −z+1/3; (iv) −x+y+1, −x+2, z+1/3; (v) y, x, −z; (vi) −x+y, −x+1, z+1/3; (vii) −y+2, x−y+1, z−1/3; (viii) −x+y, −x+1, z−2/3; (ix) −x+1, −x+y, −z−1/3; (x) y, x, −z−1; (xi) x, y, z−1; (xii) −y+2, x−y+1, z−4/3; (xiii) y, x+1, −z+1; (xiv) x, y, z+1; (xv) x−y+1, −y+2, −z+4/3; (xvi) −x+y+1, −x+2, z+4/3.

(caso4_05) top

Crystal data top

CaO_4.5SH	F(000) = 924
M_r = 145.16	D_x = 2.887 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 100 reflections
a = 17.5180 (8) Å	θ = 1–27.5°
b = 6.9291 (1) Å	µ = 2.25 mm⁻¹
c = 12.0344 (2) Å	T = 293 K
β = 133.655 (4)°	Needle, colourless
V = 1056.88 (4) Å³	0.4 × 0.08 × 0.07 mm
Z = 12

Data collection top

Bruker X8 Kappa. Apex2 diffractometer	12774 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
ω and phi scans	h = −22→22
15532 measured reflections	k = −9→9
15543 independent reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0301P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.042	(Δ/σ)_max = 0.006
wR(F²) = 0.096	Δρ_max = 0.58 e Å⁻³
S = 0.97	Δρ_min = −0.49 e Å⁻³
15543 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
193 parameters	Extinction coefficient: 0.00034 (10)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (3)

Crystal data top

CaO_4.5SH	V = 1056.88 (4) Å³
M_r = 145.16	Z = 12
Monoclinic, C2	Mo Kα radiation
a = 17.5180 (8) Å	µ = 2.25 mm⁻¹
b = 6.9291 (1) Å	T = 293 K
c = 12.0344 (2) Å	0.4 × 0.08 × 0.07 mm
β = 133.655 (4)°

Data collection top

Bruker X8 Kappa. Apex2 diffractometer	12774 reflections with I > 2σ(I)
15532 measured reflections	R_int = 0.000
15543 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.096	Δρ_max = 0.58 e Å⁻³
S = 0.97	Δρ_min = −0.49 e Å⁻³
15543 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
193 parameters	Absolute structure parameter: 0.06 (3)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ca1	0.33496 (10)	0.29588 (13)	0.57126 (16)	0.0128 (2)
Ca2	−0.16388 (10)	0.34101 (14)	0.05509 (15)	0.01086 (19)
Ca3	0.0000	0.5050 (3)	0.5000	0.0118 (3)
Ca4	0.0000	0.0014 (3)	0.0000	0.0118 (3)
S1	0.08626 (12)	0.3120 (2)	0.31005 (19)	0.0102 (3)
S2	0.24834 (5)	0.0029 (3)	0.24705 (7)	0.0084 (3)
S3	0.57935 (13)	0.3338 (2)	0.80377 (19)	0.0096 (2)
O1	0.0134 (3)	0.3877 (4)	0.3186 (4)	0.0125 (7)
O2	0.0272 (2)	0.2603 (5)	0.1521 (4)	0.0164 (8)
O3	0.1466 (2)	0.1475 (4)	0.4151 (4)	0.0177 (7)
O4	0.1659 (2)	0.4619 (4)	0.3609 (3)	0.0141 (6)
O5	0.1720 (3)	0.1210 (5)	0.1076 (4)	0.0141 (8)
O6	0.1830 (2)	0.3859 (6)	0.7602 (4)	0.0146 (8)
O7	0.3192 (3)	0.1274 (5)	0.3843 (4)	0.0146 (8)
O8	0.6651 (2)	0.1904 (4)	0.9036 (4)	0.0140 (7)
O9	0.6290 (2)	0.5187 (4)	0.8348 (3)	0.0197 (7)
O10	0.5120 (3)	0.3333 (4)	0.8354 (4)	0.0165 (8)
O11	0.5122 (2)	0.2868 (5)	0.6418 (4)	0.0153 (8)
O12	0.3171 (2)	0.3751 (6)	0.7433 (4)	0.0144 (7)
O13	0.0000	0.1599 (6)	0.5000	0.0355 (12)
O14	−0.1689 (4)	0.5093 (5)	−0.1181 (5)	0.0667 (12)
H1	−0.185 (5)	0.603 (7)	−0.151 (7)	0.100*
H2	−0.198 (5)	0.472 (8)	−0.199 (6)	0.100*
H3	0.017 (5)	0.100 (6)	0.550 (5)	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0062 (3)	0.0164 (7)	0.0127 (5)	−0.0001 (4)	0.0053 (4)	−0.0024 (4)
Ca2	0.0080 (3)	0.0111 (6)	0.0109 (4)	−0.0007 (4)	0.0056 (3)	0.0005 (3)
Ca3	0.0070 (6)	0.0190 (8)	0.0077 (7)	0.000	0.0044 (6)	0.000
Ca4	0.0060 (5)	0.0197 (8)	0.0076 (7)	0.000	0.0039 (6)	0.000
S1	0.0064 (4)	0.0134 (7)	0.0092 (6)	−0.0003 (4)	0.0048 (4)	0.0005 (4)
S2	0.0032 (6)	0.0177 (8)	0.0050 (8)	0.0009 (2)	0.0031 (6)	0.0011 (2)
S3	0.0063 (4)	0.0130 (7)	0.0084 (6)	0.0013 (5)	0.0045 (4)	0.0028 (5)
O1	0.0132 (13)	0.0142 (16)	0.0117 (13)	−0.0004 (10)	0.0092 (11)	−0.0024 (10)
O2	0.0094 (15)	0.0205 (17)	0.0148 (16)	−0.0002 (11)	0.0066 (14)	−0.0023 (12)
O3	0.0103 (14)	0.0188 (15)	0.0150 (14)	0.0090 (11)	0.0053 (12)	0.0083 (11)
O4	0.0116 (15)	0.0064 (13)	0.0208 (14)	−0.0030 (10)	0.0099 (14)	−0.0024 (10)
O5	0.0088 (14)	0.0163 (15)	0.0125 (16)	0.0044 (11)	0.0055 (13)	0.0063 (12)
O6	0.0078 (15)	0.0190 (18)	0.0183 (16)	−0.0057 (12)	0.0095 (14)	−0.0018 (12)
O7	0.0130 (15)	0.0145 (16)	0.0137 (16)	−0.0025 (12)	0.0083 (13)	−0.0062 (12)
O8	0.0011 (12)	0.0146 (14)	0.0145 (14)	0.0028 (10)	0.0010 (11)	0.0029 (10)
O9	0.0172 (16)	0.0176 (14)	0.0212 (16)	−0.0073 (11)	0.0120 (14)	−0.0043 (12)
O10	0.0122 (15)	0.019 (2)	0.0133 (13)	0.0029 (10)	0.0069 (12)	−0.0037 (10)
O11	0.0146 (16)	0.0134 (16)	0.0132 (15)	−0.0033 (12)	0.0078 (14)	−0.0030 (12)
O12	0.0048 (14)	0.0167 (16)	0.0171 (15)	0.0036 (12)	0.0058 (13)	−0.0011 (13)
O13	0.058 (3)	0.019 (3)	0.033 (3)	0.000	0.033 (3)	0.000
O14	0.161 (4)	0.0177 (18)	0.084 (3)	0.017 (2)	0.109 (3)	0.0137 (16)

Geometric parameters (Å, º) top

Ca1—O12	2.362 (4)	Ca4—O10ⁱⁱ	2.429 (4)
Ca1—O7	2.375 (4)	Ca4—O10^ix	2.429 (4)
Ca1—O3ⁱ	2.449 (3)	Ca4—O5^v	2.462 (3)
Ca1—O4ⁱⁱ	2.458 (3)	Ca4—O5	2.462 (3)
Ca1—O4	2.480 (3)	Ca4—O12^ix	2.629 (3)
Ca1—O10	2.486 (4)	Ca4—O12ⁱⁱ	2.629 (3)
Ca1—O11	2.594 (3)	Ca4—S2^v	3.1477 (7)
Ca1—O3	2.630 (3)	Ca4—S2	3.1477 (7)
Ca1—S3	3.1125 (14)	Ca4—Ca1^ix	4.0514 (19)
Ca1—S1	3.1571 (14)	Ca4—Ca1ⁱⁱ	4.0514 (19)
Ca1—Ca4ⁱⁱⁱ	4.0514 (19)	S1—O1	1.447 (4)
Ca1—Ca3^iv	4.072 (2)	S1—O2	1.448 (4)
Ca2—O14	2.336 (3)	S1—O3	1.473 (3)
Ca2—O5^v	2.406 (4)	S1—O4	1.491 (3)
Ca2—O8^vi	2.417 (3)	S2—O5	1.475 (4)
Ca2—O9ⁱⁱ	2.450 (3)	S2—O7	1.477 (4)
Ca2—O8ⁱ	2.475 (3)	S2—O6ⁱⁱ	1.502 (4)
Ca2—O6^vii	2.486 (4)	S2—O12ⁱⁱ	1.515 (4)
Ca2—O1	2.492 (4)	S2—Ca3^iv	3.1897 (7)
Ca2—O2	2.736 (3)	S3—O9	1.446 (4)
Ca2—O9^vi	2.903 (3)	S3—O11	1.457 (4)
Ca2—S1	3.1770 (14)	S3—O10	1.468 (4)
Ca2—S3^vi	3.2558 (15)	S3—O8	1.482 (3)
Ca2—Ca4	4.104 (2)	S3—Ca2^x	3.2558 (15)
Ca3—O13	2.392 (5)	O3—Ca1ⁱⁱ	2.449 (3)
Ca3—O1^vii	2.488 (3)	O4—Ca1ⁱ	2.458 (3)
Ca3—O1	2.488 (3)	O5—Ca2^v	2.406 (4)
Ca3—O11^viii	2.503 (4)	O6—S2ⁱ	1.502 (4)
Ca3—O11ⁱ	2.503 (4)	O6—Ca2^vii	2.486 (4)
Ca3—O7^viii	2.570 (3)	O7—Ca3^iv	2.570 (3)
Ca3—O7ⁱ	2.570 (3)	O8—Ca2^x	2.417 (3)
Ca3—O6^vii	2.628 (3)	O8—Ca2ⁱⁱ	2.475 (3)
Ca3—O6	2.628 (3)	O9—Ca2ⁱ	2.450 (3)
Ca3—S2^viii	3.1897 (7)	O9—Ca2^x	2.903 (3)
Ca3—S2ⁱ	3.1897 (7)	O10—Ca4ⁱⁱⁱ	2.429 (4)
Ca3—Ca1ⁱ	4.072 (2)	O11—Ca3^iv	2.503 (4)
Ca4—O2	2.365 (4)	O12—S2ⁱ	1.515 (4)
Ca4—O2^v	2.365 (4)	O12—Ca4ⁱⁱⁱ	2.629 (3)

O12—Ca1—O7	160.93 (16)	O7^viii—Ca3—S2^viii	27.08 (9)
O12—Ca1—O3ⁱ	78.52 (14)	O7ⁱ—Ca3—S2^viii	153.30 (9)
O7—Ca1—O3ⁱ	118.45 (11)	O6^vii—Ca3—S2^viii	27.84 (8)
O12—Ca1—O4ⁱⁱ	83.83 (12)	O6—Ca3—S2^viii	151.81 (8)
O7—Ca1—O4ⁱⁱ	80.13 (12)	O13—Ca3—S2ⁱ	89.74 (4)
O3ⁱ—Ca1—O4ⁱⁱ	161.00 (14)	O1^vii—Ca3—S2ⁱ	93.82 (8)
O12—Ca1—O4	90.00 (11)	O1—Ca3—S2ⁱ	86.00 (8)
O7—Ca1—O4	89.11 (11)	O11^viii—Ca3—S2ⁱ	86.66 (7)
O3ⁱ—Ca1—O4	67.43 (10)	O11ⁱ—Ca3—S2ⁱ	93.76 (8)
O4ⁱⁱ—Ca1—O4	119.93 (8)	O7^viii—Ca3—S2ⁱ	153.30 (9)
O12—Ca1—O10	70.02 (11)	O7ⁱ—Ca3—S2ⁱ	27.08 (9)
O7—Ca1—O10	119.28 (13)	O6^vii—Ca3—S2ⁱ	151.81 (8)
O3ⁱ—Ca1—O10	79.63 (10)	O6—Ca3—S2ⁱ	27.84 (8)
O4ⁱⁱ—Ca1—O10	87.81 (10)	S2^viii—Ca3—S2ⁱ	179.47 (7)
O4—Ca1—O10	144.45 (11)	O13—Ca3—Ca1ⁱ	119.67 (2)
O12—Ca1—O11	124.87 (13)	O1^vii—Ca3—Ca1ⁱ	149.03 (8)
O7—Ca1—O11	68.19 (12)	O1—Ca3—Ca1ⁱ	57.72 (8)
O3ⁱ—Ca1—O11	85.95 (11)	O11^viii—Ca3—Ca1ⁱ	91.06 (10)
O4ⁱⁱ—Ca1—O11	98.59 (11)	O11ⁱ—Ca3—Ca1ⁱ	37.75 (8)
O4—Ca1—O11	131.39 (10)	O7^viii—Ca3—Ca1ⁱ	120.77 (10)
O10—Ca1—O11	55.18 (12)	O7ⁱ—Ca3—Ca1ⁱ	33.05 (8)
O12—Ca1—O3	81.79 (12)	O6^vii—Ca3—Ca1ⁱ	111.36 (9)
O7—Ca1—O3	82.11 (11)	O6—Ca3—Ca1ⁱ	86.95 (8)
O3ⁱ—Ca1—O3	118.64 (9)	S2^viii—Ca3—Ca1ⁱ	121.05 (3)
O4ⁱⁱ—Ca1—O3	64.96 (9)	S2ⁱ—Ca3—Ca1ⁱ	59.25 (3)
O4—Ca1—O3	55.03 (8)	O2—Ca4—O2^v	81.3 (2)
O10—Ca1—O3	142.86 (9)	O2—Ca4—O10ⁱⁱ	79.47 (11)
O11—Ca1—O3	148.49 (12)	O2^v—Ca4—O10ⁱⁱ	155.56 (14)
O12—Ca1—S3	97.16 (9)	O2—Ca4—O10^ix	155.56 (14)
O7—Ca1—S3	94.68 (10)	O2^v—Ca4—O10^ix	79.47 (11)
O3ⁱ—Ca1—S3	79.62 (9)	O10ⁱⁱ—Ca4—O10^ix	122.69 (16)
O4ⁱⁱ—Ca1—S3	95.80 (7)	O2—Ca4—O5^v	70.80 (11)
O4—Ca1—S3	144.15 (8)	O2^v—Ca4—O5^v	79.52 (13)
O10—Ca1—S3	27.61 (9)	O10ⁱⁱ—Ca4—O5^v	80.00 (11)
O11—Ca1—S3	27.73 (9)	O10^ix—Ca4—O5^v	119.77 (12)
O3—Ca1—S3	160.76 (7)	O2—Ca4—O5	79.52 (13)
O12—Ca1—S1	86.44 (9)	O2^v—Ca4—O5	70.80 (11)
O7—Ca1—S1	84.02 (9)	O10ⁱⁱ—Ca4—O5	119.77 (12)
O3ⁱ—Ca1—S1	93.39 (8)	O10^ix—Ca4—O5	80.00 (11)
O4ⁱⁱ—Ca1—S1	92.47 (7)	O5^v—Ca4—O5	140.65 (18)
O4—Ca1—S1	27.46 (7)	O2—Ca4—O12^ix	126.39 (12)
O10—Ca1—S1	156.30 (9)	O2^v—Ca4—O12^ix	84.95 (11)
O11—Ca1—S1	147.58 (10)	O10ⁱⁱ—Ca4—O12^ix	94.43 (12)
O3—Ca1—S1	27.61 (7)	O10^ix—Ca4—O12^ix	66.64 (11)
S3—Ca1—S1	171.28 (5)	O5^v—Ca4—O12^ix	55.77 (12)
O12—Ca1—Ca4ⁱⁱⁱ	37.99 (8)	O5—Ca4—O12^ix	141.87 (11)
O7—Ca1—Ca4ⁱⁱⁱ	153.28 (10)	O2—Ca4—O12ⁱⁱ	84.95 (11)
O3ⁱ—Ca1—Ca4ⁱⁱⁱ	67.64 (10)	O2^v—Ca4—O12ⁱⁱ	126.39 (12)
O4ⁱⁱ—Ca1—Ca4ⁱⁱⁱ	94.04 (8)	O10ⁱⁱ—Ca4—O12ⁱⁱ	66.64 (11)
O4—Ca1—Ca4ⁱⁱⁱ	115.89 (9)	O10^ix—Ca4—O12ⁱⁱ	94.43 (12)
O10—Ca1—Ca4ⁱⁱⁱ	34.04 (8)	O5^v—Ca4—O12ⁱⁱ	141.87 (11)
O11—Ca1—Ca4ⁱⁱⁱ	87.20 (9)	O5—Ca4—O12ⁱⁱ	55.77 (12)
O3—Ca1—Ca4ⁱⁱⁱ	119.20 (8)	O12^ix—Ca4—O12ⁱⁱ	141.1 (2)
S3—Ca1—Ca4ⁱⁱⁱ	59.73 (4)	O2—Ca4—S2^v	97.89 (8)
S1—Ca1—Ca4ⁱⁱⁱ	122.46 (4)	O2^v—Ca4—S2^v	81.82 (8)
O12—Ca1—Ca3^iv	147.41 (10)	O10ⁱⁱ—Ca4—S2^v	86.01 (8)
O7—Ca1—Ca3^iv	36.16 (8)	O10^ix—Ca4—S2^v	94.17 (8)
O3ⁱ—Ca1—Ca3^iv	115.26 (8)	O5^v—Ca4—S2^v	27.14 (9)
O4ⁱⁱ—Ca1—Ca3^iv	76.84 (8)	O5—Ca4—S2^v	152.59 (9)
O4—Ca1—Ca3^iv	122.37 (8)	O12^ix—Ca4—S2^v	28.65 (8)
O10—Ca1—Ca3^iv	83.12 (8)	O12ⁱⁱ—Ca4—S2^v	151.61 (9)
O11—Ca1—Ca3^iv	36.22 (8)	O2—Ca4—S2	81.82 (8)
O3—Ca1—Ca3^iv	112.28 (9)	O2^v—Ca4—S2	97.89 (8)
S3—Ca1—Ca3^iv	59.68 (4)	O10ⁱⁱ—Ca4—S2	94.17 (8)
S1—Ca1—Ca3^iv	120.02 (4)	O10^ix—Ca4—S2	86.01 (8)
Ca4ⁱⁱⁱ—Ca1—Ca3^iv	117.13 (3)	O5^v—Ca4—S2	152.59 (9)
O14—Ca2—O5^v	69.27 (14)	O5—Ca4—S2	27.14 (9)
O14—Ca2—O8^vi	106.17 (16)	O12^ix—Ca4—S2	151.61 (9)
O5^v—Ca2—O8^vi	76.47 (11)	O12ⁱⁱ—Ca4—S2	28.65 (8)
O14—Ca2—O9ⁱⁱ	141.24 (14)	S2^v—Ca4—S2	179.62 (7)
O5^v—Ca2—O9ⁱⁱ	73.46 (12)	O2—Ca4—Ca1^ix	146.92 (10)
O8^vi—Ca2—O9ⁱⁱ	74.38 (10)	O2^v—Ca4—Ca1^ix	72.27 (10)
O14—Ca2—O8ⁱ	71.99 (12)	O10ⁱⁱ—Ca4—Ca1^ix	118.85 (9)
O5^v—Ca2—O8ⁱ	141.22 (10)	O10^ix—Ca4—Ca1^ix	34.95 (8)
O8^vi—Ca2—O8ⁱ	113.30 (9)	O5^v—Ca4—Ca1^ix	84.86 (8)
O9ⁱⁱ—Ca2—O8ⁱ	144.75 (13)	O5—Ca4—Ca1^ix	109.05 (9)
O14—Ca2—O6^vii	142.18 (14)	O12^ix—Ca4—Ca1^ix	33.58 (8)
O5^v—Ca2—O6^vii	146.91 (17)	O12ⁱⁱ—Ca4—Ca1^ix	126.80 (11)
O8^vi—Ca2—O6^vii	82.34 (12)	S2^v—Ca4—Ca1^ix	59.49 (3)
O9ⁱⁱ—Ca2—O6^vii	76.54 (12)	S2—Ca4—Ca1^ix	120.66 (3)
O8ⁱ—Ca2—O6^vii	70.88 (13)	O2—Ca4—Ca1ⁱⁱ	72.27 (10)
O14—Ca2—O1	108.46 (16)	O2^v—Ca4—Ca1ⁱⁱ	146.92 (10)
O5^v—Ca2—O1	116.07 (13)	O10ⁱⁱ—Ca4—Ca1ⁱⁱ	34.95 (8)
O8^vi—Ca2—O1	145.37 (9)	O10^ix—Ca4—Ca1ⁱⁱ	118.85 (9)
O9ⁱⁱ—Ca2—O1	78.68 (10)	O5^v—Ca4—Ca1ⁱⁱ	109.05 (9)
O8ⁱ—Ca2—O1	78.07 (11)	O5—Ca4—Ca1ⁱⁱ	84.86 (8)
O6^vii—Ca2—O1	70.42 (10)	O12^ix—Ca4—Ca1ⁱⁱ	126.80 (11)
O14—Ca2—O2	76.36 (15)	O12ⁱⁱ—Ca4—Ca1ⁱⁱ	33.58 (8)
O5^v—Ca2—O2	65.53 (11)	S2^v—Ca4—Ca1ⁱⁱ	120.66 (3)
O8^vi—Ca2—O2	138.38 (12)	S2—Ca4—Ca1ⁱⁱ	59.49 (3)
O9ⁱⁱ—Ca2—O2	78.95 (11)	Ca1^ix—Ca4—Ca1ⁱⁱ	138.84 (5)
O8ⁱ—Ca2—O2	106.99 (11)	O1—S1—O2	108.49 (19)
O6^vii—Ca2—O2	121.64 (13)	O1—S1—O3	111.41 (18)
O1—Ca2—O2	53.16 (11)	O2—S1—O3	112.0 (3)
O14—Ca2—O9^vi	73.72 (14)	O1—S1—O4	109.9 (2)
O5^v—Ca2—O9^vi	100.99 (11)	O2—S1—O4	109.19 (19)
O8^vi—Ca2—O9^vi	51.51 (8)	O3—S1—O4	105.84 (16)
O9ⁱⁱ—Ca2—O9^vi	124.64 (9)	O1—S1—Ca1	128.33 (17)
O8ⁱ—Ca2—O9^vi	65.78 (10)	O2—S1—Ca1	122.85 (16)
O6^vii—Ca2—O9^vi	84.76 (10)	O3—S1—Ca1	55.84 (12)
O1—Ca2—O9^vi	141.37 (12)	O4—S1—Ca1	50.09 (10)
O2—Ca2—O9^vi	149.98 (9)	O1—S1—Ca2	49.46 (15)
O14—Ca2—S1	94.05 (13)	O2—S1—Ca2	59.25 (14)
O5^v—Ca2—S1	90.77 (10)	O3—S1—Ca2	124.90 (14)
O8^vi—Ca2—S1	149.98 (8)	O4—S1—Ca2	128.96 (13)
O9ⁱⁱ—Ca2—S1	75.96 (8)	Ca1—S1—Ca2	177.68 (7)
O8ⁱ—Ca2—S1	93.76 (9)	O5—S2—O7	110.5 (3)
O6^vii—Ca2—S1	95.27 (8)	O5—S2—O6ⁱⁱ	111.48 (18)
O1—Ca2—S1	26.19 (9)	O7—S2—O6ⁱⁱ	106.99 (17)
O2—Ca2—S1	27.05 (9)	O5—S2—O12ⁱⁱ	105.81 (18)
O9^vi—Ca2—S1	158.41 (7)	O7—S2—O12ⁱⁱ	110.57 (18)
O14—Ca2—S3^vi	90.11 (13)	O6ⁱⁱ—S2—O12ⁱⁱ	111.6 (4)
O5^v—Ca2—S3^vi	88.08 (10)	O5—S2—Ca4	49.56 (14)
O8^vi—Ca2—S3^vi	25.16 (8)	O7—S2—Ca4	127.19 (15)
O9ⁱⁱ—Ca2—S3^vi	99.03 (8)	O6ⁱⁱ—S2—Ca4	125.67 (13)
O8ⁱ—Ca2—S3^vi	90.20 (8)	O12ⁱⁱ—S2—Ca4	56.29 (13)
O6^vii—Ca2—S3^vi	83.10 (8)	O5—S2—Ca3^iv	130.77 (16)
O1—Ca2—S3^vi	153.28 (9)	O7—S2—Ca3^iv	52.38 (14)
O2—Ca2—S3^vi	153.13 (9)	O6ⁱⁱ—S2—Ca3^iv	54.79 (13)
O9^vi—Ca2—S3^vi	26.36 (7)	O12ⁱⁱ—S2—Ca3^iv	123.37 (13)
S1—Ca2—S3^vi	174.98 (6)	Ca4—S2—Ca3^iv	179.43 (2)
O14—Ca2—Ca4	75.04 (10)	O9—S3—O11	109.22 (18)
O5^v—Ca2—Ca4	32.94 (9)	O9—S3—O10	112.6 (2)
O8^vi—Ca2—Ca4	105.74 (9)	O11—S3—O10	107.2 (2)
O9ⁱⁱ—Ca2—Ca4	67.91 (8)	O9—S3—O8	107.0 (2)
O8ⁱ—Ca2—Ca4	134.23 (7)	O11—S3—O8	111.4 (3)
O6^vii—Ca2—Ca4	139.23 (10)	O10—S3—O8	109.57 (15)
O1—Ca2—Ca4	83.32 (8)	O9—S3—Ca1	121.09 (14)
O2—Ca2—Ca4	33.45 (8)	O11—S3—Ca1	55.91 (14)
O9^vi—Ca2—Ca4	131.92 (7)	O10—S3—Ca1	51.71 (14)
S1—Ca2—Ca4	57.83 (4)	O8—S3—Ca1	131.92 (16)
S3^vi—Ca2—Ca4	120.86 (4)	O9—S3—Ca2^x	63.06 (13)
O13—Ca3—O1^vii	70.93 (8)	O11—S3—Ca2^x	124.60 (16)
O13—Ca3—O1	70.93 (8)	O10—S3—Ca2^x	126.94 (16)
O1^vii—Ca3—O1	141.86 (16)	O8—S3—Ca2^x	43.90 (13)
O13—Ca3—O11^viii	141.26 (10)	Ca1—S3—Ca2^x	175.77 (6)
O1^vii—Ca3—O11^viii	70.86 (11)	S1—O1—Ca3	143.4 (2)
O1—Ca3—O11^viii	146.89 (14)	S1—O1—Ca2	104.4 (2)
O13—Ca3—O11ⁱ	141.26 (10)	Ca3—O1—Ca2	111.67 (13)
O1^vii—Ca3—O11ⁱ	146.89 (14)	S1—O2—Ca4	141.6 (2)
O1—Ca3—O11ⁱ	70.86 (11)	S1—O2—Ca2	93.69 (18)
O11^viii—Ca3—O11ⁱ	77.5 (2)	Ca4—O2—Ca2	106.93 (12)
O13—Ca3—O7^viii	109.26 (9)	S1—O3—Ca1ⁱⁱ	144.2 (2)
O1^vii—Ca3—O7^viii	75.83 (11)	S1—O3—Ca1	96.55 (15)
O1—Ca3—O7^viii	117.41 (12)	Ca1ⁱⁱ—O3—Ca1	107.37 (11)
O11^viii—Ca3—O7^viii	66.75 (10)	S1—O4—Ca1ⁱ	124.97 (16)
O11ⁱ—Ca3—O7^viii	83.12 (13)	S1—O4—Ca1	102.46 (14)
O13—Ca3—O7ⁱ	109.26 (9)	Ca1ⁱ—O4—Ca1	111.99 (11)
O1^vii—Ca3—O7ⁱ	117.41 (12)	S2—O5—Ca2^v	140.9 (2)
O1—Ca3—O7ⁱ	75.83 (11)	S2—O5—Ca4	103.31 (19)
O11^viii—Ca3—O7ⁱ	83.12 (13)	Ca2^v—O5—Ca4	114.95 (14)
O11ⁱ—Ca3—O7ⁱ	66.75 (10)	S2ⁱ—O6—Ca2^vii	136.6 (2)
O7^viii—Ca3—O7ⁱ	141.48 (19)	S2ⁱ—O6—Ca3	97.37 (17)
O13—Ca3—O6^vii	71.69 (11)	Ca2^vii—O6—Ca3	107.34 (12)
O1^vii—Ca3—O6^vii	99.57 (12)	S2—O7—Ca1	143.6 (2)
O1—Ca3—O6^vii	68.19 (11)	S2—O7—Ca3^iv	100.54 (18)
O11^viii—Ca3—O6^vii	121.14 (12)	Ca1—O7—Ca3^iv	110.79 (14)
O11ⁱ—Ca3—O6^vii	88.45 (11)	S3—O8—Ca2^x	110.94 (17)
O7^viii—Ca3—O6^vii	54.85 (11)	S3—O8—Ca2ⁱⁱ	132.37 (18)
O7ⁱ—Ca3—O6^vii	141.53 (10)	Ca2^x—O8—Ca2ⁱⁱ	116.67 (12)
O13—Ca3—O6	71.69 (10)	S3—O9—Ca2ⁱ	145.9 (2)
O1^vii—Ca3—O6	68.19 (11)	S3—O9—Ca2^x	90.58 (15)
O1—Ca3—O6	99.57 (12)	Ca2ⁱ—O9—Ca2^x	101.83 (10)
O11^viii—Ca3—O6	88.45 (11)	S3—O10—Ca4ⁱⁱⁱ	138.4 (2)
O11ⁱ—Ca3—O6	121.14 (12)	S3—O10—Ca1	100.67 (19)
O7^viii—Ca3—O6	141.53 (10)	Ca4ⁱⁱⁱ—O10—Ca1	111.01 (13)
O7ⁱ—Ca3—O6	54.85 (11)	S3—O11—Ca3^iv	134.1 (2)
O6^vii—Ca3—O6	143.4 (2)	S3—O11—Ca1	96.36 (19)
O13—Ca3—S2^viii	89.74 (4)	Ca3^iv—O11—Ca1	106.03 (12)
O1^vii—Ca3—S2^viii	86.00 (8)	S2ⁱ—O12—Ca1	140.2 (2)
O1—Ca3—S2^viii	93.82 (8)	S2ⁱ—O12—Ca4ⁱⁱⁱ	95.06 (17)
O11^viii—Ca3—S2^viii	93.76 (8)	Ca1—O12—Ca4ⁱⁱⁱ	108.43 (13)
O11ⁱ—Ca3—S2^viii	86.66 (7)

Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) −x+1/2, y−1/2, −z+1; (iii) x+1/2, y+1/2, z+1; (iv) x+1/2, y−1/2, z; (v) −x, y, −z; (vi) x−1, y, z−1; (vii) −x, y, −z+1; (viii) x−1/2, y+1/2, z; (ix) x−1/2, y−1/2, z−1; (x) x+1, y, z+1.

Experimental details

	(caso40625)	(caso4_05)
Crystal data
Chemical formula	CaH_1.25O_4.625S	CaO_4.5SH
M_r	147.40	145.16
Crystal system, space group	Trigonal, P3₂21	Monoclinic, C2
Temperature (K)	296	293
a, b, c (Å)	13.8690 (4), 13.8690 (4), 12.7189 (1)	17.5180 (8), 6.9291 (1), 12.0344 (2)
α, β, γ (°)	90, 90, 120	90, 133.655 (4), 90
V (Å³)	2118.70 (9)	1056.88 (4)
Z	24	12
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	2.24	2.25
Crystal size (mm)	0.4 × 0.08 × 0.07	0.4 × 0.08 × 0.07

Data collection
Diffractometer	Bruker X8 Kappa. Apex2 diffractometer	Bruker X8 Kappa. Apex2 diffractometer
Absorption correction	Numerical	–
T_min, T_max	0.641, 0.896	–
No. of measured, independent and observed [I > 2σ(I)] reflections	38925, 3252, 2578	15532, 15543, 12774
R_int	0.043	0.000

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.03	0.042, 0.096, 0.97
No. of reflections	3252	15543
No. of parameters	260	193
No. of restraints	5	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	–
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.45	0.58, −0.49
Absolute structure	Flack H D (1983), Acta Cryst. A39, 876-881	Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	0.00	0.06 (3)

Computer programs: Apex2, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), Diamond 3.

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